利用线性酚醛树脂制备有序介孔碳

三嵌段共聚物F127为模板剂,线性酚醛树脂为碳前驱体,采用溶剂挥发诱导有机-有机自组装法(EI-SA)制备了具有二维六方结构的有序介孔碳。利用FT-IR、XRD、TEM、N2吸附/脱附等方法对有序介孔碳的结构进行了表征,研究了不同焙烧温度和模板剂用量对有序介孔碳结构的影响。结果表明,当模板剂的用量一定时,有序介孔碳的孔径、孔容和孔壁厚度都随着焙烧温度的升高而降低,但比表面积却随着微孔含量的增加而增大。随着模板剂用量的增加,介孔碳的有序性降低。有序介孔碳PF-2-500的比表面积、孔径、孔容、孔壁厚度和微孔比表面积比分别为583.82m2/g、3.05nm、0.31cm3/g、3.40nm和361.18m2/g,而有序介孔碳PF-1-500的比表面积、孔径和孔容相对于PF-2-500有所提高,分别为647.79m2/g、3.44nm和0.41cm3/g,但微孔比表面积和孔壁厚度分别降低为309.46m2/g和3.35nm。     

Recent Progress in the Synthesis of Porous Carbon Materials

In this review, the progress made in the last ten years concerning the synthesis of porous carbon materials is summarized. Porous carbon materials with various pore sizes and pore structures have been synthesized using several different routes. Microporous activated carbons have been synthesized through the activation process. Ordered microporous carbon materials have been synthesized using zeolites as templates. Mesoporous carbons with a disordered pore structure have been synthesized using various methods, including catalytic activation using metal species, carbonization of polymer/polymer blends, carbonization of organic aerogels, and template synthesis using silica nanoparticles. Ordered mesoporous carbons with various pore structures have been synthesized using mesoporous silica materials such as MCM‐48, HMS, SBA‐15, MCF, and MSU‐X as templates. Ordered mesoporous carbons with graphitic pore walls have been synthesized using soft‐carbon sources that can be converted to highly ordered graphite at high temperature. Hierarchically ordered mesoporous carbon materials have been synthesized using various designed silica templates. Some of these mesoporous carbon materials have successfully been used as adsorbents for bulky pollutants, as electrodes for supercapacitors and fuel cells, and as hosts for enzyme immobilization. Ordered macroporous carbon materials have been synthesized using colloidal crystals as templates. One‐dimensional carbon nanostructured materials have been fabricated using anodic aluminum oxide (AAO) as a template.     

Ordered Mesoporous Carbons

Ordered mesoporous carbons have recently been synthesized using ordered mesoporous silica templates. The synthesis procedure involves infiltration of the pores of the template with appropriate carbon precursor, its carbonization, and subsequent template removal. The template needs to exhibit three‐dimensional pore structure in order to be suitable for the ordered mesoporous carbon synthesis, otherwise disordered microporous carbon is formed. MCM‐48, SBA‐1, and SBA‐15 silicas were successfully used to synthesize carbons with cubic or hexagonal frameworks, narrow mesopore size distributions, high nitrogen Brunauer–Emmett–Teller (BET) specific surface areas (up to 1800 m² g^–1), and large pore volumes. Ordered mesoporous carbons are promising in many applications, including adsorption of large molecules, chromatography, and manufacturing of electrochemical double‐layer capacitors.     

新型两亲性嵌段共聚物导向合成有序大孔径介孔材料的研究进展

自从1992年首次报道介孔氧化硅分子筛M41S系列以来, 人们采用各种商业化表面活性剂为模板, 合成了多种骨架组成、丰富的有序介观结构、不同孔径尺寸的介孔材料, 并将其应用在能源、环境、催化等诸多领域。然而, 由于常规商业化模板剂的分子量大小有限, 合成的介孔材料具有较小的孔径(< 8.0 nm), 从而极大地限制了其面对大尺寸客体分子的相关应用。此外, 利用常规模板剂难以合成出具有晶化墙壁的介孔金属氧化物材料。近年来, 大分子量两亲性嵌段共聚物相继被报道用来合成新型介孔材料, 本文将综述基于这种嵌段共聚物为模板剂合成各种具有大孔径和晶化墙壁介孔材料的研究进展。     

Bio-inspired synthesis of mesoporous sílicas using large molecular weight poly-l-lysine at neutral pH

Among the various types of amorphous silica-based materials, those that have mesopores (pore widths between 2 and 50 nm) constitute an important group. Silica mesoporous materials have been considered in fields such as catalysis, adsorption, sensing, and electronics or, more recently in drug delivery. The synthesis of silica mesoporous materials usually involves corrosive reaction media and high temperatures. Nevertheless, some living organisms such as diatoms or sponges produce silica in non-corrosive environments and at ambient temperatures. Important progress has been achieved in the synthesis of silica-based materials by biomimetic or bio-inspired methodologies, but the number of studies that use biomolecules and address specifically the preparation of mesoporous materials is reduced. We report in this work, to our knowledge for the first time, a methodology to obtain mesoporous silicas that involves, simultaneously, a biomolecule (poly-l-lysine) and neutral pH. The prepared materials have pores with widths between 2 and 8 nm and specific surface areas between 232 and 616 m² g^?1.     

Mesoporous Silica Thin Membranes with Large Vertical Mesochannels for Nanosize‐Based Separation

Membrane separation technologies are of great interest in industrial processes such as water purification, gas separation, and materials synthesis. However, commercial filtration membranes have broad pore size distributions, leading to poor size cutoff properties. In this work, mesoporous silica thin membranes with uniform and large vertical mesochannels are synthesized via a simple biphase stratification growth method, which possess an intact structure over centimeter size, ultrathin thickness (≤50 nm), high surface areas (up to 1420 m² g^?1), and tunable pore sizes from ≈2.8 to 11.8 nm by adjusting the micelle parameters. The nanofilter devices based on the free‐standing mesoporous silica thin membranes show excellent performances in separating differently sized gold nanoparticles (>91.8%) and proteins (>93.1%) due to the uniform pore channels. This work paves a promising way to develop new membranes with well‐defined pore diameters for highly efficient nanosize‐based separation at the macroscale.     

One-pot synthesis of ordered mesoporous carbon–silica nanocomposites templated by mixed amphiphilic block copolymers

Mixed amphiphilic block copolymers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO–PPO–PEO) and polydimethylsiloxane-poly(ethylene oxide) (PDMS–PEO) have been successfully used as co-templates to prepare ordered mesoporous polymer–silica and carbon–silica nanocomposites by using phenolic resol polymer as a carbon precursor via the strategy of evaporation-induced self-assembly (EISA). The ordered mesoporous materials of 2-D hexagonal (p6m) mesostructures have been achieved, as confirmed by small-angle X-ray scattering (SAXS), transmission electron microscopy (TEM), and nitrogen-sorption measurements. Experiments show that using PDMS–PEO as co-template can enlarge the pore sizes and reduce the framework shrinkage of the materials without evident effect on the specific surface areas. Ordered mesoporous carbons can then be obtained with large pore sizes of 6.7 nm, pore volumes of 0.52 cm³/g, and high surface areas of 578 m²/g. The mixed micelles formed between the hydrophobic PDMS groups and the PPO chains of the F127 molecules should be responsible for the variation of the pore sizes of the resulting mesoporous materials. Through the study of characteristics of mesoporous carbon and mesoporous silica derived from mother carbon–silica nanocomposites, we think mesoporous carbon–silica nanocomposites with the silica-coating mesostructure can be formed after the pyrolysis of the PDMS–PEO diblock copolymer during surfactant removal process. Such method can be thought as the combination of surfactant removal and silica incorporation into one-step. This simple one-pot route provides a pathway for large-scale convenient synthesis of ordered mesostructured nanocomposite materials.     

Hierarchically porous carbons with partially graphitized structures for high rate supercapacitors

Partially graphitized hierarchically porous carbons (denoted as GHPCs) were prepared by using ordered mesoporous nickel oxide as template. The mesoporous nickel oxide, which is different from the inert template such as mesoporous silica SBA-15, plays an important role in the synthesis of the carbons with partially graphitized nanostructures at high temperature. X-ray diffraction, transmission electron microscopy and nitrogen adsorption were employed to characterize the structure of GHPCs. It is shown that the GHPC obtained by calcinating the precursor at 700 °C has a hierarchically porous structure with the pore size distributions at 8 and 30 nm. Partially graphitized structure leads to the high electrical conductivity of GHPCs. The GHPC prepared at 700 °C (GHPC700) shows outstanding high rate performance. Its specific capacitance reaches 91 F g^?1 at a potential scan rate of 500 mV s^?1. Meanwhile the specific capacitance for the GHPC prepared at 600 °C (GHPC600) is only 46 F g^?1 at the same scan rate. Synergistic effect of the efficient ion transport in hierarchically porous structure and the high electrical conductivity owing to the partially graphitic structure is contributed to the attractive electrochemical performance of GHPC700.     

水热法合成介孔氧化硅材料的结构及表面特性

以十六烷基三甲基溴化氨 (CTMABr)为模板剂 ,利用碱性水热法制备了介孔氧化硅材料 ,并采用小角度XRD、HRTEM、BET和FT IR等测试手段研究了其孔的结构、表面N2 吸附特性和孔径分布情况。结果表明 :碱性水热法制得的介孔氧化硅材料具有规则的六方结构 ,介孔的最可几半径为 1 9mm ,比表面积为 5 42 8m2 / g ,孔容为 0 4 5 6cm3/ g。     

以嵌段共聚物为结构导向剂的SBA-15和SBA-16的合成及表征

利用嵌段共聚物P123和F127分别在强酸性条件下合成了两种结构不同的介孔氧化硅材料:一维直孔道六方相的SBA-15和三维立方相的SBA-16,并通过XRD、N₂吸附-脱附、HTEM等手段对材料进行了研究。结果表明:商品化的嵌段共聚物作为结构导向剂合成的介孔氧化硅材料SBA-15和SBA-16孔道规整有序,比表面积分别达到765m²·g^-1和930m²·g^-1,相应的最可几孔径分别为6.46nm和3.92nm,这有利于介孔材料向经济实用方向发展。     

气-液界面二元共沉积法制备三维有序大孔SiO2

采用乳液聚合法制备粒径为229nm的单分散聚苯乙烯(PS)微球,以单分散PS微球和粒径为10nm的硅溶胶为原料,采用蒸发自组装法在气-液界面上二元共沉积,制备了大孔SiO2材料。结果表明,当SiO2体积分数为11%时,大孔SiO2材料呈现有序规整的FCC结构,其填充率为42%,收缩率仅为2%。低温N2吸附表明该材料在大孔孔壁上存在6.4nm左右的介孔,是一种具有大孔/介孔复合孔道结构的功能材料。     

乙烯基修饰的微孔二氧化硅膜孔结构与疏水性研究

在溶胶-凝胶反应过程中, 用乙烯基三乙氧基硅烷(TEVS)代替部分正硅酸乙酯(TEOS), 通过两者共水解缩合反应制备乙烯基修饰的SiO₂膜, 并通过BET、TG、NMR、以及接触角测量仪对所制备的材料进行表征. 结果表明: 修饰后的二氧化硅膜仍保持微孔结构, 且孔径集中分布在0.5～0.7nm之间. 由于部分亲水表面羟基被疏水乙烯基团所代替, 乙烯基修饰的SiO₂膜疏水性能得到明显提高, 并且随着TEVS加入量的增加, 疏水性能逐渐增强.     

Effect of solution pH on the surface morphology of sol–gel derived silica gel

We have examined the effect of solution acidity on the textural characteristics of silica gels prepared by sol–gel synthesis using tetraethyl orthosilicate (TEOS) as a silica precursor and cetyltrimethylammonium bromide (CTAB) as a template. Using IR spectroscopy, we have studied micellar TEOS solutions and the synthesized silica gel samples. The results demonstrate that, in an alkaline medium in a water–ethanol solution, SiO₂ experiences short-range ordering on the surface of micelles formed by CTAB molecules, whereas in an acid medium the process is not influenced by the presence of CTAB. Nitrogen porosimetry and electron microscopy data indicate that the silica gel obtained at pH 2 is microporous, with an average pore size of 2 nm. In an alkaline medium at pH 10, we obtained mesoporous SiO₂ (18 nm) with a narrow pore size distribution and a specific surface area of 110 m²/g.     

Synthesis of ordered mesoporous Pd/carbon catalyst with bimodal pores and its application in water-mediated Ullmann coupling reaction of chlorobenzene

Heterogeneous palladium catalysts have been supported on the ordered mesoporous carbons (Pd/OMC) with bimodal pores which are prepared by the surfactant-templating approach. Characterization using XRD, TEM, XPS, H₂ chemisorption, and N₂ sorption techniques reveals that the Pd/OMC catalysts have the ordered 2-D hexagonal mesostructure (space group of p6mm), extremely high surface areas (~1800 m²/g), large pore volumes (~1.64 cm³/g), bimodal pores (6.3 nm of primary mesopores and 1.7 nm of secondary mesopores inside the pore walls), hydrophobic carbon surface, and small metal particles well-dispersed inside the secondary small mesopores. This catalyst exhibits a high yield of 43% for biphenyl from the Ullmann coupling reaction of chlorobenzene in water at 100 °C without assistance of any phase transfer catalyst and can be reused up to 10 times, providing potential opportunities for industrial applications such as coupling and hydrogenation reactions.     

Reflectance of surfactant-templated mesoporous silica thin films: Simulations versus experiments

In this study, cubic and hexagonal mesoporous amorphous silica thin films were synthesized using evaporation-induced self-assembly process followed by calcination leaving highly ordered spherical or cylindrical pores in a silica matrix. The films featured pores with diameter between 4 and 11 nm, lattice parameter from 7.8 to 24 nm, and porosity between 22% and 45%. All films were dehydrated prior to reflectance measurements except for one film which was fully hydrated. The present study compares the spectral reflectance measured experimentally between 400 and 900 nm with that computed numerically by solving three-dimensional Maxwell's equations in mesoporous silica thin films with the same morphology as those synthesized. The matrix was assumed to have the same optical properties as bulk fused silica. The pore optical properties were either those of air or liquid water whether the film was dehydrated or hydrated, respectively. Excellent agreement was found between experimental and numerical reflectance for both cubic and hexagonal mesoporous silica films. This study experimentally validates our simulation tool and offers the prospect of ab-initio design of nanocomposite materials with arbitrary optical properties without using effective medium approximation or mixing rules.     

Preparation of ordered 2-D hexagonal mesoporous silica with ultra thick pore walls using a novel nonionic organosilicon surfactant

Mesoporous silica was synthesized by modified nonionic organosilicon surfactant under acidic condition for the first time. The XRD patterns, HRTEM image and corresponding BET characterization show that it has ordered 2-D hexagonal pore channel and ultra thick pore wall (about 6 nm). The calcination can result in the vanishment of organic composite and the linkage of the hydrolyzed silica source and the hydrophobic chain (polymethylsiloxane) of the silica-based template. Hence this recombination process tremendously enhances the pore wall of the resulting mesoporous material and causes a certain amount of micropores in the wall. The resulted mesoporous material has high hydrothermal stability due to its ultra thick pore wall and hydrophobic surface.     

Mesoporous silica obtained by polycondensation of octahydridooctasilsesquioxane

Mesoporous silica, due to its porosity and morphological features, have been considered a fascinating material for many technological applications. In this report, we describe the preparation of a structurally stable mesoporous silica material using octahydridooctasilsesquioxane (T₈ ^H). The structure and properties of final samples were determined by XRD, FT-IR, and TEM methods. Structural analysis has shown that the siliceous material is amorphous but mesoporous. BET surface area, pore volumes, and pore size distribution were measured using nitrogen sorption methods—data were collected from the adsorption branch using BJH method for mesopores and t-plot method for micropores. It was found that the cage-type structure of T₈ ^H molecules and the process conditions determine the specific morphology of the cross-linked products. Completely inorganic, mesoporous silica of a narrow pore distribution was obtained. It was found that the materials have large surface area and pores in the meso range (2–5 nm). The amount of mesopores and the characteristic surface area of the prepared samples strongly depended on the reaction conditions.     

Polyethyleneimine-functionalized large pore ordered silica materials for poorly water-soluble drug delivery

Four ordered mesoporous silica supports with different pore structure characteristics were investigated for their drug loading and release abilities with regard to their structural variabilities as well as implications of surface modification. The (model) drug molecule in question was the poorly water-soluble glucocorticoid Prednisolone, composed of a steroid skeleton with functional groups in the form of carbonyls and hydroxyls. Under non-aqueous conditions, such as those applied for drug loading, these functional groups are expected to interact with the surface silanols of the silica supports, but this interaction could possibly also be enhanced by introducing amino groups to the silica surfaces. Thus, all four supports were further functionalized by surface hyperbranching of polyethyleneimine), PEI, which was successfully incorporated to all supports in high amounts (>30 wt%). However, the accessibility of the pore system after organic modification was dependent on the pore sizes and structures, highlighting the importance of using large-pore mesophases with adequate structures when aiming for applications involving (bulky) guest molecules. Additionally, after incorporation of large amounts of guest molecules (40 wt%), full water accessibility was retained in that the loaded cargo could be rapidly released from the carrier matrixes, which is a crucial requirement when formulating poorly soluble substances. Results displayed that the release of Prednisolone from the silica supports occurred faster than the dissolution of the pure drug. All silica materials released more than 85 % of the adsorbed drug in 5 h, independently of the support material. Thus, the confinement of Prednisolone inside the mesopores seems to be the main reason for the faster kinetic release rate. These constraints imply that Prednisolone becomes more mobile inside the pores, and therefore more soluble in release medium. These results confirm the potential of silica supports as drug delivery carriers for drugs with limited water solubility such as steroids.     

介孔SiO2孔道结构对聚酰胺反渗透复合膜性能的影响

在界面聚合过程中,通过添加改进水热方法制备的球形介孔SiO2纳米材料,制备了改性的聚酰胺反渗透复合膜。使用扫描电镜、X射线衍射和氮气吸附-脱附等手段对制备的介孔SiO2纳米材料进行表征;采用反渗透膜评价装置、原子力显微镜、扫描电镜(SEM)和静态接触角仪器等手段对复合膜的性能和结构进行测试和表征;并对比了相同粒径大小的实心SiO2和介孔SiO2对膜渗透性能的影响。结果证明:成功合成了一种具有孔径分布均匀、粒径均一、比表面积较大、分散性较好的介孔SiO2纳米球形颗粒;SEM表征结果证实纳米材料在膜表面分布均匀,膜表面亲水性能提高,粗糙度变大;膜性能测试结果证实了介孔SiO2的添加使得膜在维持较高截留率的前提下,具有更高的水通量;同时,通过对比相同尺寸的实心SiO2作为添加材料,证实了介孔SiO2的孔道结构更有利于水分子的传输。当介孔SiO2添加质量为0.06%时,水通量由23L/(m2·h)提高至39L/(m2·h),对氯化钠的截留仍然维持在98%以上。     

The size-controllable synthesis of nanometer-sized mesoporous silica in extremely dilute surfactant solution

10–60 nm-sized mesoporous silica particles with ordered or worm-like pore structures were controllably synthesized in extremely dilute surfactant solution, and the lowest concentrations of TEOS and CTAB were 12.45 mM, 1.52 mM, respectively. The synthesis of nanometer-sized Al-incorporated mesoporous silica particles (Al-MS) was also performed under the similar conditions. Compared to the mesoporous silica without doping of aluminum, those Al-incorporated silica particles have a certain textural mesoporosity. The results indicate that the size and pore structure of mesoporous silica can be adjusted by changing the concentration of reactants. The mesoporous silica nanoparticles, including Al-MS, were characterized by transmission electron microscopy (TEM), small-angle X-ray diffraction (SAXRD), as well as nitrogen adsorption/desorption techniques. It was suggested that the formation of the mesoporous silica nanoparticles could be attributed to the deposition of self-assembled silicate micelles.